Fluorine removal process



F. E. FREY Filed oct. 16, 1944 ATroRNEYs v FLORINE REMOVAL PRocEss anhydrous, or about 99 t0 Patented Dec. 17, 1946 Frederick Frey,

Bartlesville, Okla.,

assignor to Phillips Petroleum Company, a corporation of Delaware Application October 16, 1944, Serial No. 558,941

Claims.

This invention relates to the treatment o'f organic materials to remove therefrom organic fluorine-containing compounds. In one general embodiment it relates to the remo'val from hydrocarbon materials of ilumine-containing compounds. In one of its specific embodiments this invention relates to the removal of both hydrogen fluoride and of organically vbound uorine from hydrocarbon mixtures such as are produced b y alkylation.

In the presence of suitable catalysts, alkylatable hydrocarbons react with unsaturated hydrocarbons or other suitable alkylating reactants to produce higher boiling hydrocarbons. which is known as alkylation..l is promoted especially well by hydrouoric acid. This catalyst yields excellent results with isoparafns or other branched chain parains and particularly parafns with at least one tertiary carbon atom per molecule and with olefins having more-than two carbon atoms per molecule. However, under especially favorable circumstances othervparaflns and/or olefns may react. Besides paraflins, other alkylatable hydrocarbons, such as aromatic hydrocarbons, can vbe reacted with an alkylating reactant in the presence of hydroiluoric acid to produce higher boiling hydrocarbons. Suitable alkylatin'g` reactants for the alkylation of either parafiinsor aromatics include olens, relatively polar nonprimary alkyl compounds, such as tertiary and secondary alkyl halides, advantageously uorides andA chlorides,

The reaction,

alcohols, and the like.`

The hydrouoric acid preferably should be above about 80 per cent in strength and will generally be used with a strength greater than 90 per cent; it is most advantageous when it is substantially 100 per cent in strength.

Because of its nonoxiding character, hydrofluoric acid does not produce the oxidation byy products that are formed in alkylation with such catalysts as sulfuric acid. Furthermore, hydrofluric acid is relatively free from the tendency to form complex tarry addition products that are formed in alkylation with certain other catalysts.

However, hydroiiuoric acid is appreciably soluble' in saturated hydrocarbons and itsI use as a catalyst solutions of`sodium hydroxide or sodium carbonate. Some of them apparently are the alkyl uorides which result from the addition of hydrogen fluoride to the olefin used as the alkyla'ting reactant, o r to replacement yof a hydroxyl group or of another halogen atom by fluorine when other akylatingreactants such as alcohols or chlorides are used in the alkylation reaction. These have boiling points which are not substantially higher than the corresponding oleflns. Other organic ilumine-containing compounds are higher boiling and are to be found in various fractions which have boiling points throughout the usually accepted motor fuel boiling range, that is. up to about 400 F. The various organicuorine-containing compounds tend to decompose at elevated temperatures, especially the higher boiling ones, and often decompose `during fractional distillation of the hydrocarbon products, thereby contributing to the problems of commercial operation, particularly problems relating to the combating and control of corrosion in distillation equipment.

,.Iikewise, their presence in motor fuel products decreases Vthe desirable characteristics of such products. f

. practice irst to remove presents a problem of recovery that is not involved when other catalysts are used.

In such alkylation processes smalll proportions of organic fluorine-containing by-products are also formed. Generally the entire hydrocarbon mixture which can be separated from'eiiluents of such an alkylation will contain organically bound fluorine in an amount not greater than about 1 per cent by weight, and often the amount /will InsomeA commercial operations wherein alkylation is utilized to produce large quantities of hydrocarbons in the motor fuel range it iscommon dissolved free hydrogen fluoride from hydrocarbon eliluents of the alkylation and subsequently toA treat the entire hydrocarbon mixture to remove all organic iluorine compounds therefrom. Since a large portion of these compounds correspond to the original a1ky1.. ating reactants and can be returned to the alkylation step as a part of the charged alkylating reactant, such treatment often includes the removal of uorine from unnecessary quantities of the organic impurities. In other instances such a hydrocarbon mixture, after the removal of free hydrogen fluoride is subjected to fractional distillation to separate various hydrocarbon fractions .and one' or more of the alkylate fractions are been definitely established,

can be eiected ing a substantial portion of the same lfractional distillation,

, selective removal substantially Iriad-between about desired, particularly when a normal paraflin is `one of the alkylation reactants, a small yamount through pipe I3 ration is effected between hydrocarbon eii'luents,`

I removed through pipe acier/ae I tional'tr'eating equipment is necessary toeffect removal of such free hydrogen fluoride.

I I have now found that eflicient removal of higher-boiling organic-fluorine-containing compounds by a dehydroiluorination and free hydrogen fluoride so. produced can be removed emciently, together with removalof free hydrogen uoride which carbon eiliuents of the alkylation step, by vaporizsuch hydrocarbon eilluents so that most or all of the dissolved hydrogen fluoride and a large portion of in part to alkylation zone I I. Generally it isalso desirable to pass a portion of this used. catalyst -to puriication equipment, not shown, through pipe-IB.y The liquid hydrocarbon mixture which is dissolved in liquid hydrounreacted hydro'carbons, together with low-boiling alkyl' fluorides, are removed as vapors, the unvaporized I i residue is treated to effect a removal of organically combined iiuorine, preferably in a dehydrofluorination step, eiiuents of this treatment are passed to a fractional distillation, vaporsfrom the vaporization step are cooled and condensed and passed to and a hydrocarbon material free from free hydrogen fluoride and free from high-boiling organic uorine compounds is-recovered as a'high-boiling product of said distillation. l

- An object of this invention is to effect removal oi iluorine from hydrocarbon materials containing-organic fluorine compounds as impurities.

A further object of this invention is an imfor alkylate vfrom the alkylation of hydrocarbons in the presence of a catalyst comprising hydrogen fluoride. l

Another object of organic fluorine compounds from other organic materials.

A further object of higher-boiling iiuorlne compounds from eilluents of an alkylation process. Other objects and advantages of my invention will become apparent to one skilled in theart from the accompanying disclosure and discussion.

my invention is to remove.

of my invention is to effect a 50 per cent' by volume. of unreacted isobutane,

obtaining a substantially My invention will now be furtherdiscussed and illustrated by a specific embodimentthereof, in

connection with the'accompanying drawing showing diagrammatically an arrangement of apparatus which maybe used in the practice ferred modification of my process.'

A suitable hydrocarbon charge, such as an isoexample, the molar ratio of isobutane to butylenes will be between about 3:1 and about 10:1, the

' liquid volume ratio of hydrocarbons to hydrofluoric acid catalyst will be materials will bev intimately admixed peraturejof about at a temto F. for a reaction pe- 5 and about20 minutes. If

of boron triiluoride may be added as a promoter,

generally in an amount between about 1 and about 10 per cent by weight of the hydroiiuoric acid catalyst. Eiiluents of alkylatlon zone I I are passed to separator Il wherein a sepapreferably as a liquid hydrocarbon mixture, and liquid hydrofluoric acid. The hydrofiuoric acid is tionator 25.

of a preabout 1:1 and these I4 will comprise a subunreacted reactant, low-boilis separated in separator stantial amount of fing hydrocarbons such as isobutane, an appreciable but minor amount of normally liquid hydrocarbons produced by the .alkylation process,

va small but dennite amount of dissolved hydrogen uoride and a stilll smaller amount of iluorine present as organic fluorine compounds. i As an example, when isobutane is alkylated with butenes in the presence of concentrated hydrofluoric acid as the valkylation catalyst a total hydrocarbon phase has been obtained which contains well over about 10 to 20 per cent by volume of alkylate, between about 0.3 and 2.0 per cent by weight of dissolved hydrogen fluoride, and between about 0.01' and about 0.15 weight per cent of fluorine present as'organicall'y bound fluorine, of which half to two-thirds is present as butyl-fluorides. Such a liquid mixture is passed through pipe I1 to flash chamber 20 wherein a vaporization of a large portion ofthe more volatile constituents is eiected, including substantially al1 of the dissolved free hydrogen fluoride. It is generally desirableto supply a substantial amount of heat to aid in .this vaporization. This may be obtained by passing .the liquid hydrocarbon material through heater I8 and/or by means of a. heating coil I9 in the bottom of flashchamber 20. Satisfactory operation is generally obtained by a sim- -ple vflashing with separation of vapors through pipe 2I and of liquid through pipe 22. However, in some instances it may be found more desirable to ald this flashing by including a small amount of conventional packing, or a few bubble trays, s0 as to insure substantially complete absence of alkylate from the vapors passing through pipe 2I and to reduce the amount of low-boiling hydrocarbons, such. as butane, present in the unvaporized liquid passing through pipe,k 22. This unvaporized liquid will contain substantially all of the alkylate, together with higher-boiling organic fluorine compounds which are deleterious to the alkylate, This material is passed through dehydrouorimator 23 wherein it is treated un-` der suitable dehydrofluorination conditions, such as will be morefully discussed hereinafteig'to decompose these organic hydrocarbons and free fluents of through pipe-24 to fractionator 25, which may be a, single fractional distillation column. In such a case-these eflluents are preferablypassed to an intermediate portion o f the column.

Vapors from flash chamber 20 are passed through pipe 2| and cooler and condenser` 26 to an accumulator 21, which may serve as a simple surge tank for the resulting condensate. However, since this material contains substantially all of the hydrogen fluoride contained in the hydrocarbons passing through pipe I1 vand has an hydrogen fluoride. Ef-

l appreciable smaller content of hydrocarbons in I5 and is returned-'at least 75v rdistillation most instances'a separate liquid hydrouoric acid phase often forms in accumulator 2.1. If such is the case this separates and can be removed through pipe 30 and can be 'returned to separator Il. The liquid hydrocarbon material collected in accumulator 21 and containing dissolved'hydrogen fluoride ispassed through pipe 3l to frac- When fractionator 25 is a single column, as previously discussed,A this fluorine compounds into the dehydrofluorination are passed J liquid hydrocarbon stream can be added near the two molecules of isobutane unite to form 'an p of the column as a liquid redux. Heat for the octane, a portion of this isobutane recycle stream distillation may be furnished by a suitable heatmay be diverted from pipe 45 through pipe 45 to lng means, illustrated by heating coil 32. Any depropanizer 41. A low-boiling fraction comuncondensed vapors, such as a propane-hydr 5 prising propane is discarded from the system gen uoride mixture, may be removed from acthrough pipe 48 and a puriied isobutane stream cumulator 2l through pipe 28 and passed .to pipe is -returned to pipe 45 through pipe 49. 3 An alkylate fraction is removed from the bot- A low-boiling fraction comprising all of the tom of debutanizer 4I and may be passed through free hydrogen fluoride which is present, both in pipe 50 to rerun column 5I wherein a light alkylthe stream passing through pipe 24 and in the ate fraction is separated from a heavier alkylate stream passing through pipe 3|, is removed fraction. This light alkylate fraction may be rethrough pipe 33 and may be passed through covered for use as amotor fuel stock through pipe cooler and condenser 34 and pipe 35 to pipe 4I3 52 and a heavy alkylate fraction is recovered. and separator I4. As more fully discussed in through pipe 53. my Patent 2,322,800, issued June 29, 1943, this It will be readily appreciated by thos skilled material will be accompanied by an appreciable in the art thatthe drawing illustrates th;;\u5e oi" amount of low-boiling hydrocarbons. If desired, conventional equipment which is not sho in a portion of this vapor stream may be diverted detail, and that much conventional equipment from pipe 33 through pipe 36 to heating coil i9 in 20 such as heaters, coolers, condensers, reflux equiporder to supply heat to the vaporizing material ment, pumps, compressors, catalyst chambers, in flash chamber and the material, somewhat and the like, will be necessary in the practice or cooled by the vaporlzation taking place in iiash any specific embodiment of my invention and chamber 20, is returned to pipe 33 through pipe can readily be adapted' by one skilled in the art 31. Also, if desired, a portion of the cooled and in the light of the teachings vand discussion-precondensed overhead product trom fractionator 25 sented herein. may be passed to accumulator 21 through .pipe The iiashing of volatile constituents can be 38.A conducted most simply by heating the liquid ma- From the botto mof..1'ractionator 25 a hydroterial passing through pipe I'l, in heater I8, and carbon mixture, which is substantially free from passing the heated stream into a simple ilash free hydrogen iiuoride and is also substantially chamber. Thus, when isobutane present in a free from higher-boiling organic iluorine coml butane mixture is reacted with butylenes present pounds, is recovered and is treated to separate in a refinery butane-butylene fraction, in the various desired fractions.' Thus it may be passed presence of a hydroiiuoric acid alkylation catathrough pipe 40 to debutanizer "whereinnor- 35 lyst, the :liquid hydrocarbon effluent separated mal butane and lighter hydrocarbons are sepafrom the catalyst has a composition as shown in rated from heavier normally liquid hydrocarbons, the rst column of the accompanying table, atea including' the alkylate produced in the alkylation lseparation temperature of about 88 F. and a zone Il. The low-boiling fraction fro'm debupressure of about 35 pounds gage. When this tanizer 4I is passed through pipe 42 to deisobu- 40 material is heated to about 100 F. and flashed, in tanizer 43. From the bottom of deisobutanizer a simple flash chamber, down to this same pres- 43 normal butane is recovered through pipe 44 sure, the amount of material vaporized and refor any subsequent. treatment as may b'e desired, maining liquid, and the composition of the vapor such as dehydrogenation to `olens for use in and liquid, will be as shown in the table under alkylation zone Il and/or isomerization into iso- 45 the heading'corresponding to this temperature. butane for use in alkylation zone Il. From the Similar data vare also shown for heating'. the top of deisobutanizer 43 an is"obutane fraction is stream to 105 F.and to 115 F. prior to -ilashing.

. A 100 F. 105 F. 115 F. Liquid Mol per cent of emuent 100 Vapor Liquid Vapor Liquid Vapor Liquid 45 68 32 Composition:

Propane 5. 3 8.9 2. 7 7. 6 2. 4 6. 9 l. 9 Isobutan 33. 3 40. 0 28. 5 29. 4 25. 8 38. 5 22. 1 N. butano... 46. 6 46. 3 46.8 48. 7 44.1 50.0 39. 2 Isopentene. l. 5 0. 9 l. 9 0. 9 2. 2 l. 2 2.. 2

0.7 0.2 1.0 0.4 1.1 0.4 1.3 l 10.5 0. 0 18. 1 0. 2 23.2 0.6 31. 9 0.4 0.0 0.7 0.0 0.9. 0.0 1.2 1.6 3.6 0.2 2. 7 0.2 2.3 0. 1 iluorides 0.1 0. 1(-) 0. l(+) 0. l 0. l 0. l(+) 0.1()

removed through pipe 45 and may be recycled to A somewhatmore desirable separation is eilected alkylation zone i This fraction will comprise 00 by supplying .a substantial portion of the heat of Aan appreciable amount of butyl fiuorides present vaporization to the bottom oi the flash chamber,

in emuents oil the alkylation zone, since these will as by means of a heating coil I9. By the use have been vaporized in flash chamber 20 and will of only twoor three bubble-trays the amount of' not have been subjected to a dehydroiluorination. n butane and lighter (including hydrogen iluoride) Since, incommercial processes, some propane will U present in the liquid and of pentanes in the tend -to accumulate in the system, particularly if vapors, particularly at the higher-temperatures,

`propylene or propyl fluoride ls present in the can be decreased without adding greatly to the charge to the alkylation step and if the reaction expense of the operation. As will be appreciconditions are such that this propylene or propyl ated, such a vflashing operation can also be aided fluoride takes up hydrogen to form propane as by means ofa pump in pipe 22 and of a com- 'of catalyst per hour.

conditions can be readily determined Y pending application hydrogen fluoride .at a

' nickel, cobalt, zirconium,

vanadium. manganese, thorium, tungsten, urapresser in pipe 2| whereby ilash chamber 20 can be operated at a lower pressure than subsequent equipment. Although the amount of organic iluorides in the vapor and in the liquid phases in the preceding dashing operations are not markedly different, the vaporized fluorides are primarily volatile compounds which can be satisfactorily recycled and the unvaporized'compounds are undesirable compounds normally present in the alkylate.A l

The dehydrofluorination step is conducted by passing the hydrocarbon material' which contains organic ilumine-,containing impurities into contact with a suitable dehydrouorination catalyst under conditions such that most, or all, of the organic fiuorine compounds are decomposed to form iluorine-free compounds and free hydrogen fluoride. 'This can generally be accomplished by passing the impure hydrocarbon material either in the liquid or vapor phase, preferably in the liquid phase, through the catalyst at a space velocity of 1 to 10 volumes of liquid per volume -The temperature in the catalyst chamber is preferably between 150 and 350 F., but temperatures as low as 75 F. and as high as 750 F. or higher may be used. The pressure is preferably sufcient to drocarbon in the liquid phase. For treating any particular impure hydrocarbon material optimum by trial, in the light of the discussion and disclosure presented herein.

The dehydrofluorination catalyst is preferablycontained in a suitable catalyst chamber as a mass of solid granular material, although other modifications of using vsolid catalysts which are known in the oil cracking art or the like may be employed if desired. As the dehydrofluorination catalyst various alkaline earth fiuorides, various metals such as aluminum, magnesium, iron or the fluorides nickel or salts of such metals such as or sulfates may be used. Catalysts which are particularly active and useful in the practice of my process are the oxides of metals which have been treated with hydrogen fluoride as has been more fully disclosed and Serial N0. 510,203, filed November 13, 1943. These novel catalytic materials are prepared by treating various oxides of metals with hydrogen fluoride, or with a materialwhich will release hydrogen vfluoride under the conditions used for treating the metal oxide. An especially a more or less hydrous oxide o aluminum with suitable temperature. Other desirable catalysts can be produced by similar treatment of oxides of iron, chromium, molybdenum, titanium,

nium, hafnium, or the like, alone or in admixture. synthetically produced or in natural occurring forms, as in ores. ring oxides, Isuch as bauxite, limonite, manganite, baddeleyite, brookite, brucite, diaspore, dysanalite,'gibbsite, goethite, hausmannite, huebnerite, ilmenite, lepidocrocite, rutile, spinel, valentinite, etc. itis generally desirable to choose an ore relatively free from substantial' amounts of silica. although minor amounts are not deleterious, and often are advantageous, since a more porous giranular material results 'from removal of the s lica. v This treatment is preferably carried out at a temperature between about 50 and about 350 F.

discussed byme in my co desirable catalyst results from treating v complete, dehydration erally will ldrofiuoric acid for a period ofseveral be available in a more or less hydrous condition. After such dehydration be treated directly with liquidconcentrated hyhours. Too results in a less active catalyst, too long a. treatment often has the result that the original granules disintegrate to the extent that the resulting material has too low a mechanical strength for handling. It is often more convenient to place the granular oxide in the catalyst short a treatment chamber and to pass through the granular mass dehydrofluorination catalyst. Still another pre-y maintain the hy- When using naturally occur- One method is to effect a substantial, but not 7 azeotropicy mixture a stream of liquid concentrated hydrofluoric acid, or a hydrocarbon stream containing tree hydrogen uoride. Bauxite or other granular oxide material, which has been used in the manner disclosed in my Patent can also be employed as' a dehydroiluorination catalyst. However, it is 'generally desirable to give the used oxide material a further treatment with hydroduoric acid before employing it asa ferred dehydrofluorination catalyst is produced from yellowish ferrie oxide either limonite or in the form resulting from the oxidation with air of wet iron. Such ainaterial should then be treated with hydrogen fluoride as previously discussed. It will be readily appreciated that various modil fications, and embodiments of my invention may skilled in the art, by following the teachings of the present disclosure without departing from the spirit thereof or from the scope of the claims. l

I claim:

1. `In a process for reacting. isobutane with a butylene under alkylation conditions in the presence of a hydrofluoric acid alkylation catalyst, the improvement which comprises passing 'efiluents of suchan alkylation to a separating zone and separating as a liquid the hydrocarbon content thereofi from liquid hydrofluoric acid, pass-` ing a resulting liquid hydrocarbon material containing dissolved hydrogen distillation'zone, cooling and condensing said vaporizeddissolve'd hydrogen fluoride and unreacted isobutane and passing a resulting isobutane-containing condensate to said4 distillation zone, and recovering tional distillation zone a low-boiling fraction comprising free hydrogen fluoride together with at least a suiiicient-quantity of a normally gaseous paraiiin hydrocarbon to form a minimum-boiling therewith and as a high-boiling fraction a hydrocarbon material free from from said frachydrogen iluoride and comprising unreacted isobutane and alkylate.

2. In a process for the reaction of an alkylating reactant with a low-boiling parailin hydrocarbon in the presence of a hydrofluoric acid alkylation catalyst,- the improvement which comprises passing etlluents of such an alkylation to a separating zone and separating as a liquid a hydrocarbon phasefrom liquid hydrofluoric acid, passing a resulting liquid of the oxide, which gen-- the oxide may" 2,347,945, isslld May 2, 1944,

in the form of fluoride to va flash L vaporization zone under conditions that substan- Y tially all saiddissolved hydrogen 'nuoride and a fractional hydrocarbon material containing dissolved hydrogen iiuoride to a vaporization zone and vaporizing same therein under condi- .unvaporized material to a dehydrouorination to decompose organic uorine compounds contained therein as impuritiesforming hydrocarbons and 10 free hydrogen uoride, passing eiliuents of said dehydrouorination to a fractional distilla- I tion zone, cooling and condensing said vaporized dissolved hydrogen fluoride and unreacted hydrocarbons and passing a resulting hydrocarbon- 15 containing condensate to said fractional distillation zone, and removing from said fractional distilla'tion zone a low-boiling fraction comprising free hydrogen uoride and as a high-boiling fraction a hydrocarbon material comprising unre- 20 acted parafiins and alkylate.

3. A process for the removal of small amounts of dissolved hydrogen uoride and high-boiling said dissolved vhydrogen Ii-uoride and a substantial portion of said low-boiling hydrocarbons are vaporized and such as to leave unvaporized highboiling hydrocarbons and high-boiling organic.

comprising hydrogen fluorideand a high-boiling fraction comprising both low-boiling and highboiling hydrocarbons and substantially free from free hydrogen Iluoride and high-boiling organic iiuorine compounds.

4. In a process for alkylating a low-boiling par\ 50 ailinhydrocarbon in the presence of a hydroporizing said material under conditions such that substantially all of said dissolved hydrogen iluo- 60 ride and a substantial portion of said unreacted railin hydrocarbons are vaporized and substantially all ofy said alkylate together with high-boiling organic fiuorine compounds remain unvaride phase, passing said liquid hydrocarbon phase to said fractional distillation as a reflux stream, and recovering from said fractional distillation a.

from free hydrogen iluoride. 5. In a. process for the reaction of an alkylatcarbon material comprising unreacted isoparaf-4 

